EP2847365B1 - Sulfate scale control in low ph aqueous systems - Google Patents
Sulfate scale control in low ph aqueous systems Download PDFInfo
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- EP2847365B1 EP2847365B1 EP13787749.4A EP13787749A EP2847365B1 EP 2847365 B1 EP2847365 B1 EP 2847365B1 EP 13787749 A EP13787749 A EP 13787749A EP 2847365 B1 EP2847365 B1 EP 2847365B1
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- scale
- scale control
- ppm
- bhmtap
- control agent
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title description 12
- YWMWZKYVGNWJPU-UHFFFAOYSA-N [bis[6-[bis(phosphonomethyl)amino]hexyl]amino]methylphosphonic acid Chemical group OP(=O)(O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(=O)O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O YWMWZKYVGNWJPU-UHFFFAOYSA-N 0.000 claims description 60
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 230000002378 acidificating effect Effects 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 16
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 230000002401 inhibitory effect Effects 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 description 46
- 230000000996 additive effect Effects 0.000 description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- 230000005764 inhibitory process Effects 0.000 description 23
- 238000012360 testing method Methods 0.000 description 19
- 239000011575 calcium Substances 0.000 description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 14
- 229960005069 calcium Drugs 0.000 description 14
- 229910052791 calcium Inorganic materials 0.000 description 14
- 239000013078 crystal Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 10
- 230000003278 mimic effect Effects 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 5
- -1 calcium Chemical class 0.000 description 5
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 5
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 5
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- NEVBYCDQGXFCCZ-UHFFFAOYSA-N 1-propylpyrido[2,3-d][1,3]oxazine-2,4-dione Chemical compound C1=CC=C2C(=O)OC(=O)N(CCC)C2=N1 NEVBYCDQGXFCCZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical group CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 229910000385 transition metal sulfate Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BCXBKOQDEOJNRH-UHFFFAOYSA-N NOP(O)=O Chemical class NOP(O)=O BCXBKOQDEOJNRH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- UIQZDQSTZWGFMX-UHFFFAOYSA-H dialuminum octadecan-1-ol trisulfate Chemical compound C(CCCCCCCCCCCCCCCCC)O.S(=O)(=O)([O-])[O-].[Al+3].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].[Al+3] UIQZDQSTZWGFMX-UHFFFAOYSA-H 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-M ethenesulfonate Chemical compound [O-]S(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-M 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
- C02F5/145—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus combined with inorganic substances
Definitions
- the invention relates to inhibition of hard, adherent deposit formation of insoluble metal salts particularly sulfates of metals such as calcium, and/or other alkaline earth metals, in presence of late transition metals in low pH aqueous systems, i.e. highly acidic aqueous systems.
- insoluble metal salts particularly sulfates of metals such as calcium, and/or other alkaline earth metals
- late transition metals in low pH aqueous systems, i.e. highly acidic aqueous systems.
- organic phosphonates are used, either alone or with inorganic phosphonates and/or polymeric dispersants for scale control in aqueous systems.
- Certain organic and inorganic phosphonates have been used, either alone or with polymers, as scale control or inhibition agents but the effectiveness of such phosphonates is limited to systems having pH above 4 or 5. Additionally, low molecular weight polymeric scale control agents, including those bearing carboxylic acid or sulfonic acid functionality, typically perform very poorly in low pH systems which can be attributed to the low dissociation constants (pKa) of such polymers. Because conventional scale control agents have operational limits with respect to pH, phosphonate based agents including those comprising phosphonate and polymer, for use in highly acidic systems, such as those having pH less than about 4, to suppress scale deposition, including by threshold inhibition or crystal habit modification, are highly desired.
- scale control agents would be useful in mining applications which involve wide ranges of pH, temperature, and pressure depending on the type of ore subjected to mineral processing.
- US2002/094299 discloses the use of scale control agents comprising organic phosphonates for inhibiting scale formation or deposition in acidic aqueous systems.
- the scale control agents comprising bis(hexamethylenetriaminepenta (methylenephosphonic acid)) (BHMTAP) are applied to inhibit hard, adherent deposit formation of insoluble metal salts particularly sulfates of metals such as calcium, and/or other alkaline earth metals in presence of late transition metals.
- BHMTAP bis(hexamethylenetriaminepenta (methylenephosphonic acid))
- These agents may be applied on filter presses, weeping lines for heap leaches, pipes, holding vessels, evaporators, heat exchangers, cooling towers, boilers, autoclaves, or other sites that induce scale deposit formation in industrial processes.
- the scale control agents comprise bis(hexamethylenetriaminepenta (methylenephosphonic acid)) (BHMTAP) either alone or in combination with inorganic phosphonates and/or polymeric dispersants.
- the scale control agent may further comprise polymers, such as low molecular weight polymeric dispersants.
- These additives are effective at scale control, such as inhibiting metal sulfate nucleation in highly acidic aqueous systems that may also have high concentrations of hardness, chloride, sulfate, organics, dissolved transition metals or corrosion inhibitors or insoluble solids or operate at high temperature, and pressure. These agents suppress calcium sulfate deposition through threshold inhibition and also by altering crystal morphology.
- the invention also concerns processes for inhibiting and/or removing scale from the surface of a substrate, such as process equipment, comprising adding the scale control agent to a highly acidic aqueous system in an effective amount to inhibit scale formation or deposition on a surface in contact with the highly acidic aqueous system.
- a substrate such as process equipment
- the term "low pH aqueous systems" or “highly acidic aqueous systems” means those aqueous systems having pH less than 2, including less than 1; including all points within these specified ranges.
- the invention relates to the use of bis(hexamethylenetriaminepenta (methylenephosphonic acid)) (BHMTAP) for scale inhibition in highly acidic aqueous systems, such as process waters having soluble transition metals, high concentrations of hardness, sulfates, chlorides, organics, and salts.
- the scale control agents comprise bis(hexamethylenetriaminepenta (methylenephosphonic acid)) (BHMTAP) and polymer, and may optionally comprise inorganic phosphonate.
- the invention further relates to processes for the inhibition of and/or removal of scale deposits, such as calcium sulfate scale, comprising adding the scale control agent to a highly acidic system, having a pH of 2 or less in an effective amount to inhibit the formation of scale on a surface in contact with the highly acidic aqueous system.
- the organic phosphonate is added to the highly acidic system in amounts of 10 parts per million (ppm) to 100 ppm preferably 10 ppm to 50 ppm and may be added in amounts of 5 ppm to 25 ppm.
- the organic phosphonate used in the scale control agent is bis(hexamethylenetriaminepenta (methylenephosphonic acid))(BHMTAP).
- the low molecular weight polymeric dispersant typically comprises polymers derived from unsaturated monomers bearing one or more of the following functionalities: carboxylic acid, sulfonic acid, phosphonic acid, alcohol or amide, and their respective salts.
- Organic phosphonates bearing an alkyl amine spacer were employed alone and in combination with low molecular weight polymeric dispersants to inhibit calcium sulfate scale formation or deposition.
- the efficacy of organic phosphonates was studied and results are listed in Table 1.
- the efficacies of phosphonates alone were tested using highly acidic mimic process water having 5,000 ppm of calcium (as CaCO 3 ), 20,000 ppm of sulfate and 3,700 ppm of chloride ion.
- Solution A was prepared by dissolving 14.7 g of calcium chloride dihydrate and 0.713 g of anhydrous sodium chloride to a total volume of 1 liter using deionized (DI) water.
- DI deionized
- Solution B was prepared by dissolving 14.306 g of anhydrous sodium sulfate and 31.32 g of concentrated sulfuric acid to a total volume of 1 liter using deionized (“DI") water.
- DI deionized
- an appropriate amount of the scale control additive was added to 50 mL of solution A and mixed thoroughly. The pH of the test water was maintained between 0.9-1.1.
- 50 mL of solution B was added and mixed for 2 hours at the desired temperature.
- the solutions were filtered and the filtrate was titrated with 0.2 M EDTA-Na 4 solution using CalVer 2 as indicator to determine the soluble calcium concentration.
- Table 1 Table.
- Solution C was prepared by dissolving 14.7 g of calcium chloride dihydrate and 12.2 g of 1 N hydrochloric acid to a total volume of 1 liter using DI water.
- Solution D mixed element water was prepared by dissolving metal sulfate of iron sulfate heptahydrate 0.7 g, aluminum sulfate octadecylhydrate 0.33 g, copper sulfate pentahydrate 2.72 g, manganese sulfate monohydrate 0.22 g and 40.32 g of concentrated sulfuric acid to a total volume of 1 liter using DI water.
- an appropriate amount of the scale control additive was added to 50 mL of solution C and mixed thoroughly. The pH of the test water was maintained between 0.9 - 1.1. To this mixture, 50 mL of solution D was added and mixed for 2 hours at the desired temperature.
- Table 2 shows, performance of these phosphonates in presence of transition metal sulfates present in mimic water. Under the conditions listed in Table 2, DETPMPA and HMDTMPA experienced an effect in performance when evaluated with mimic waters containing soluble salts of transition metals. Whereas, changing the water chemistry of mimic test water, BHMTAP efficacy did not change significantly.
- Solution E was prepared by dissolving 14.7 g of calcium chloride dihydrate and 0.713 g of anhydrous sodium chloride to a total volume of 1 liter using DI water.
- Solution F was prepared by dissolving 14.306 g of anhydrous sodium sulfate and 31.32 g of concentrated sulfuric acid to a total volume of 1 liter using DI water.
- an appropriate amount of the scale control additive was added to 50 mL of solution E and mixed thoroughly. The pH of the test water was maintained between 0.9 - 1.1. To this mixture, 50 mL of solution F was added and mixed for 2 hours at the desired temperature.
- the effect of hardness was studied by varying the calcium ion concentration in water.
- the concentration of calcium, chloride and sulfate ion in solution G and H were maintained in such a way that on mixing 50 mL of each solution can lead into desired concentration of individual ion and pH in the test water.
- an appropriate amount of the scale control additive was added to 50 mL of solution G and mixed thoroughly.
- 50 mL of solution H was added and mixed for 2 hours at the desired temperature.
- the solutions were filtered and the filtrate was titrated with 0.2 M EDTA-Na 4 solution using CalVer 2 as indicator to determine the soluble calcium concentration. The results of these tests are shown in Fig.
- Mimic waters with 5,000 ppm calcium as calcium carbonate, 20,000 ppm sulfate, and 7,000 ppm chloride were prepared.
- Solution J was prepared by dissolving 14.7 g of calcium chloride dihydrate and 0.713 g of anhydrous sodium chloride to a total volume of 1 liter using DI water.
- Solution K was prepared by dissolving 14.306 g of anhydrous sodium sulfate and 31.32 g of concentrated sulfuric acid to a total volume of 1 liter using DI water.
- 1% solutions of desired metal sulfate Al, Cu, Fe, Mn and Zn were prepared by dissolving respective amount of metal sulfate in 100 mL DI water.
- Low molecular weight polymeric dispersant and BHMTAP blend The performance of low molecular weight polymeric dispersant and BHMTAP blend was evaluated.
- Low molecular weight polymers derived from one or more than one of the following monomers vinyl sulfonate (SVS), allyl sulfonates (SAS), acrylic acid (AA), vinyl phosphonic acid and maleic acid (MA) or their salts were synthesized.
- Blends of above mentioned polymers or commercial polymer KEMGUARD® 269 with BHMTAP with three different ratios of 1:3, 1:1 and 3:1 w/w were prepared and their performances were evaluated using mimic process water with 8,800 ppm Ca as CaCO 3 , 20,000 ppm sulfate and 7,400 ppm of chloride ion.
- Solution L was prepared by dissolving 25.1 g of calcium chloride dihydrate and 4.28 g of anhydrous sodium chloride to a total volume of 1 liter using DI water.
- Solution M was prepared by dissolving 14.31 g of anhydrous sodium sulfate and 31.32 g of concentrated sulfuric acid to a total volume of 1 liter using DI water.
- an appropriate amount of the scale control additive was added to 50 mL of solution L and mixed thoroughly. The pH of the test water was maintained between 0.9 - 1.1.
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- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Detergent Compositions (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
Description
- The invention relates to inhibition of hard, adherent deposit formation of insoluble metal salts particularly sulfates of metals such as calcium, and/or other alkaline earth metals, in presence of late transition metals in low pH aqueous systems, i.e. highly acidic aqueous systems. In particular organic phosphonates are used, either alone or with inorganic phosphonates and/or polymeric dispersants for scale control in aqueous systems.
- Increased maintenance costs, decreased plant throughput, equipment downtime and safety are a few problems associated with scale deposition in industrial processes. The deposition and accumulation of inorganic salts on surfaces, due to changes in temperature, pressure, or pH, lowers equipment efficiency and facilitates corrosive processes. In many instances, these deposits are hard and need to be removed manually, which creates additional safety concerns and also adds significant cost due to production downtime. In recent years, there has been an increasing demand for chemicals to remove soluble salts, suppress precipitation or alter the crystal morphology to avoid deposition.
- Certain organic and inorganic phosphonates have been used, either alone or with polymers, as scale control or inhibition agents but the effectiveness of such phosphonates is limited to systems having pH above 4 or 5. Additionally, low molecular weight polymeric scale control agents, including those bearing carboxylic acid or sulfonic acid functionality, typically perform very poorly in low pH systems which can be attributed to the low dissociation constants (pKa) of such polymers. Because conventional scale control agents have operational limits with respect to pH, phosphonate based agents including those comprising phosphonate and polymer, for use in highly acidic systems, such as those having pH less than about 4, to suppress scale deposition, including by threshold inhibition or crystal habit modification, are highly desired. Such scale control agents would be useful in mining applications which involve wide ranges of pH, temperature, and pressure depending on the type of ore subjected to mineral processing.
US2002/094299 discloses the use of scale control agents comprising organic phosphonates for inhibiting scale formation or deposition in acidic aqueous systems. - The scale control agents comprising bis(hexamethylenetriaminepenta (methylenephosphonic acid)) (BHMTAP) are applied to inhibit hard, adherent deposit formation of insoluble metal salts particularly sulfates of metals such as calcium, and/or other alkaline earth metals in presence of late transition metals. These agents may be applied on filter presses, weeping lines for heap leaches, pipes, holding vessels, evaporators, heat exchangers, cooling towers, boilers, autoclaves, or other sites that induce scale deposit formation in industrial processes.
- The scale control agents comprise bis(hexamethylenetriaminepenta (methylenephosphonic acid)) (BHMTAP) either alone or in combination with inorganic phosphonates and/or polymeric dispersants. The scale control agent may further comprise polymers, such as low molecular weight polymeric dispersants. These additives are effective at scale control, such as inhibiting metal sulfate nucleation in highly acidic aqueous systems that may also have high concentrations of hardness, chloride, sulfate, organics, dissolved transition metals or corrosion inhibitors or insoluble solids or operate at high temperature, and pressure. These agents suppress calcium sulfate deposition through threshold inhibition and also by altering crystal morphology. The invention also concerns processes for inhibiting and/or removing scale from the surface of a substrate, such as process equipment, comprising adding the scale control agent to a highly acidic aqueous system in an effective amount to inhibit scale formation or deposition on a surface in contact with the highly acidic aqueous system. As used in this specification the term "low pH aqueous systems" or "highly acidic aqueous systems" means those aqueous systems having pH less than 2, including less than 1; including all points within these specified ranges.
- All parts and percentages set forth in this specification and the appended claims are on a weight by weight basis unless otherwise specified.
-
-
Fig. 1 is a graph showing the effect of water hardness on bis(hexamethylenetriaminepenta (methylenephosphonic acid))BHMTAP performance. -
Fig. 2 is a scanning electron microscope image of calcium sulfate crystal morphology with no additive treatment. -
Fig. 3 is a scanning electron microscope image of calcium sulfate crystal morphology treated with 100 parts per million (ppm) BHMTAP in accordance with an embodiment of the invention. -
Fig. 4 is a scanning electron microscope image of calcium sulfate crystal morphology treated with 50 ppm of scale control agent in accordance with an embodiment of the invention comprising KEMGUARD® 269 polymer (available from Kemira, Helsinki, Finland) and BHMTAP (Additive C). -
Fig. 5 is a scanning electron microscope image of calcium sulfate crystal morphology treated with 50 ppm of scale control agent in accordance with an embodiment of the invention comprising polymer of acrylic acid/maleic acid (poly(AA/MA)) and BHMTAP (Additive A). - The invention relates to the use of bis(hexamethylenetriaminepenta (methylenephosphonic acid)) (BHMTAP) for scale inhibition in highly acidic aqueous systems, such as process waters having soluble transition metals, high concentrations of hardness, sulfates, chlorides, organics, and salts. Typically the scale control agents comprise bis(hexamethylenetriaminepenta (methylenephosphonic acid)) (BHMTAP) and polymer, and may optionally comprise inorganic phosphonate. The invention further relates to processes for the inhibition of and/or removal of scale deposits, such as calcium sulfate scale, comprising adding the scale control agent to a highly acidic system, having a pH of 2 or less in an effective amount to inhibit the formation of scale on a surface in contact with the highly acidic aqueous system. Typically, the organic phosphonate is added to the highly acidic system in amounts of 10 parts per million (ppm) to 100 ppm preferably 10 ppm to 50 ppm and may be added in amounts of 5 ppm to 25 ppm.
- The organic phosphonate used in the scale control agent is bis(hexamethylenetriaminepenta (methylenephosphonic acid))(BHMTAP). The low molecular weight polymeric dispersant typically comprises polymers derived from unsaturated monomers bearing one or more of the following functionalities: carboxylic acid, sulfonic acid, phosphonic acid, alcohol or amide, and their respective salts.
- Organic phosphonates bearing an alkyl amine spacer were employed alone and in combination with low molecular weight polymeric dispersants to inhibit calcium sulfate scale formation or deposition. The efficacy of organic phosphonates was studied and results are listed in Table 1. The efficacies of phosphonates alone were tested using highly acidic mimic process water having 5,000 ppm of calcium (as CaCO3), 20,000 ppm of sulfate and 3,700 ppm of chloride ion. Solution A was prepared by dissolving 14.7 g of calcium chloride dihydrate and 0.713 g of anhydrous sodium chloride to a total volume of 1 liter using deionized (DI) water. Solution B was prepared by dissolving 14.306 g of anhydrous sodium sulfate and 31.32 g of concentrated sulfuric acid to a total volume of 1 liter using deionized ("DI") water. For scale control testing, an appropriate amount of the scale control additive was added to 50 mL of solution A and mixed thoroughly. The pH of the test water was maintained between 0.9-1.1. To this mixture, 50 mL of solution B was added and mixed for 2 hours at the desired temperature. On completion, the solutions were filtered and the filtrate was titrated with 0.2 M EDTA-Na4 solution using CalVer 2 as indicator to determine the soluble calcium concentration. The results of these tests are summarized in Table 1.
Table. 1: Effect of organic phosphonates on calcium sulfate scale inhibition No. Additive Dose, ppm Temperature, °C % Inhibition 1 Blank 0 50 48 2* ATMP 100 50 52 3* ATMP 200 50 56 4* DETPMPA 10 50 55 5* DETPMPA 25 50 69 6* HMDTMPA 10 50 78 7* HMDTMPA 25 50 99 8* BHMTAP 5 50 90 9 BHMTAP 10 50 99 *Reference Example - Tests performed with no scale control additive resulted in formation of calcium sulfate precipitate. Amino trimethylene phosphonic acid (ATMP) bearing three phosphonic acid groups showed increased inhibition compared to the blank control but had less inhibition than the other tested acids. Diethylenetriaminepentakis (methylphosphonic acid) (DETPMPA) containing five methyl phosphonic acid functionalities separated by ethylene diamine units showed better performance when compared with ATMP and the blank control. Use of phosphonates, hexamethylene diamine tetra (methylene phosphonic acid) (HMDTMPA) and bis(hexamethylenetriaminepenta(methylenephosphonic acid)), (BHMTAP) having six carbon spacer length showed the best performance. While the mechanism of scale inhibition by use of organic phosphonate has not been elucidated, the inventors without wishing to be bound by theory propose the efficacy of organic amino phosphonates is dependent on alkyl spacer length between nitrogen and phosphorus atom and also on number of methyl phosphonic acid groups.
- The efficacy of DETPMPA, HMDTMPA and BHMTAP in highly acidic mimic waters containing acidified solution of transition metal sulfates (Al, Cu, Fe, Mn etc) was studied. Solution C was prepared by dissolving 14.7 g of calcium chloride dihydrate and 12.2 g of 1 N hydrochloric acid to a total volume of 1 liter using DI water. Solution D mixed element water was prepared by dissolving metal sulfate of iron sulfate heptahydrate 0.7 g, aluminum sulfate octadecylhydrate 0.33 g, copper sulfate pentahydrate 2.72 g, manganese sulfate monohydrate 0.22 g and 40.32 g of concentrated sulfuric acid to a total volume of 1 liter using DI water. For scale control testing, an appropriate amount of the scale control additive was added to 50 mL of solution C and mixed thoroughly. The pH of the test water was maintained between 0.9 - 1.1. To this mixture, 50 mL of solution D was added and mixed for 2 hours at the desired temperature. On completion, the solutions were filtered through 45 micron syringe filter and filtrates were analyzed by using inductively coupled plasma - atomic emission spectroscopy (ICP-AES). The threshold inhibition was calculated by using following formula:
- Where, CaSITU is amount of calcium in filtrate
- CaBLK is amount of calcium measured for filtrate obtained with no additive treatment
- CaTOTAL is amount of calcium in test water
- Table 2 shows, performance of these phosphonates in presence of transition metal sulfates present in mimic water. Under the conditions listed in Table 2, DETPMPA and HMDTMPA experienced an effect in performance when evaluated with mimic waters containing soluble salts of transition metals. Whereas, changing the water chemistry of mimic test water, BHMTAP efficacy did not change significantly.
- The effect of temperature on BHMTAP performance was evaluated. Solution E was prepared by dissolving 14.7 g of calcium chloride dihydrate and 0.713 g of anhydrous sodium chloride to a total volume of 1 liter using DI water. Solution F was prepared by dissolving 14.306 g of anhydrous sodium sulfate and 31.32 g of concentrated sulfuric acid to a total volume of 1 liter using DI water. For scale control testing, an appropriate amount of the scale control additive was added to 50 mL of solution E and mixed thoroughly. The pH of the test water was maintained between 0.9 - 1.1. To this mixture, 50 mL of solution F was added and mixed for 2 hours at the desired temperature. On completion, the solutions were filtered and the filtrate was titrated with 0.2 M EDTA-Na4 solution using CalVer 2 as indicator to determine the soluble calcium concentration. The results of these tests are summarized in Table 3
Table 3: Effect of temperature on BHMTAP performance No. Additive Dose, ppm Temperature, ° C % Inhibition 1 Blank 0 25 39 2* BHMTAP 5 25 45 3 BHMTAP 10 25 79 4 BHMTAP 25 25 99 5 Blank 0 50 48 6* BHMTAP 5 50 90 7 BHMTAP 10 50 99 8 Blank 0 70 66 9* BHMTAP 5 70 90 10 BHMTAP 10 70 99 *Reference Example - The solubility of calcium sulfate in water is temperature dependent. The lower the temperature tested under these conditions, the stronger the thermodynamic driving force for precipitation. Thus, increasing amounts of calcium sulfate precipitation were observed with decreasing temperature. When solutions were charged with 10 ppm of additive at 25 °C, small amount of precipitate was observed after 2 hours. Similarly, the titrations performed on the filtrate suggested 79% of calcium remained in the solution. Further increase in additive concentration to 25 ppm showed no precipitate formation over 2 hours and titration of filtrate also shows 99% inhibition (Table 3). Further, when a similar experiment was performed at 70 °C, the temperature at which calcium sulfate is more soluble than ambient temperature, 10 ppm of BHMTAP additive was sufficient enough to achieve quantitative inhibition over 2 hours.
- The effect of hardness was studied by varying the calcium ion concentration in water. The concentration of calcium, chloride and sulfate ion in solution G and H were maintained in such a way that on mixing 50 mL of each solution can lead into desired concentration of individual ion and pH in the test water. For scale control testing, an appropriate amount of the scale control additive was added to 50 mL of solution G and mixed thoroughly. To this mixture, 50 mL of solution H was added and mixed for 2 hours at the desired temperature. On completion, the solutions were filtered and the filtrate was titrated with 0.2 M EDTA-Na4 solution using CalVer 2 as indicator to determine the soluble calcium concentration. The results of these tests are shown in
Fig. 1 which shows the plot of BHMTAP concentration as a function of threshold inhibition for water with three different levels of hardness. Increasing calcium ion concentration from 5,000 ppm to 8,800 ppm demands significantly higher dosage of additive to achieve quantitative inhibition. Runs performed using water with increased calcium concentration and lower sulfate concentration also require 25 ppm of additive to reach up to 97% inhibition. - The effect of transition metal ions on BHMTAP performance was studied. Mimic waters with 5,000 ppm calcium as calcium carbonate, 20,000 ppm sulfate, and 7,000 ppm chloride were prepared. Solution J was prepared by dissolving 14.7 g of calcium chloride dihydrate and 0.713 g of anhydrous sodium chloride to a total volume of 1 liter using DI water. Solution K was prepared by dissolving 14.306 g of anhydrous sodium sulfate and 31.32 g of concentrated sulfuric acid to a total volume of 1 liter using DI water. 1% solutions of desired metal sulfate (Al, Cu, Fe, Mn and Zn) were prepared by dissolving respective amount of metal sulfate in 100 mL DI water. For scale control testing, an appropriate amount of the scale control additive (10 ppm) and metal sulfate solution were added to 50 mL of solution J and mixed thoroughly. The pH of the test water was maintained between 0.9 - 1.1. To this mixture, 50 mL of solution K was added and mixed for 2 hours at the desired temperature. On completion, the solutions were filtered through 45 micron syringe filter and filtrates were analyzed by using inductively coupled plasma- atomic emission spectroscopy (ICP-AES). The threshold inhibition was calculated by using formula applied in Example 2.
Table 4: Effect of metal sulfates on BHMTAP performance at 50 °C Expt. 1 Expt. 2 Expt. 3 Expt. 4 Expt. 5 Al (ppm) % I Fe (ppm) % I Cu (ppm) % I Zn (ppm) % I Mn (ppm) % I 0 99 0 99 0 99 0 99 0 99 25 98 100 99 1000 82 100 99 50 99 50 96 200 99 1500 81 250 99 100 99 100 98 500 39 - 500 99 200 89 - As shown in table 4, individual solution of metal sulfate salts were added to the mimic water discussed above to obtain a solution with desired concentration of each metal. The amount of additive added for each experiment was maintained as 10 ppm. The data presented in table 4 suggest higher concentrations of iron and copper affect the additive performance. Whereas, aluminum, manganese and zinc did not demonstrate appreciable change in BHMTAP performance.
- The performance of low molecular weight polymeric dispersant and BHMTAP blend was evaluated. Low molecular weight polymers derived from one or more than one of the following monomers vinyl sulfonate (SVS), allyl sulfonates (SAS), acrylic acid (AA), vinyl phosphonic acid and maleic acid (MA) or their salts were synthesized. Blends of above mentioned polymers or commercial polymer KEMGUARD® 269 with BHMTAP with three different ratios of 1:3, 1:1 and 3:1 w/w were prepared and their performances were evaluated using mimic process water with 8,800 ppm Ca as CaCO3, 20,000 ppm sulfate and 7,400 ppm of chloride ion. Solution L was prepared by dissolving 25.1 g of calcium chloride dihydrate and 4.28 g of anhydrous sodium chloride to a total volume of 1 liter using DI water. Solution M was prepared by dissolving 14.31 g of anhydrous sodium sulfate and 31.32 g of concentrated sulfuric acid to a total volume of 1 liter using DI water. For scale control testing, an appropriate amount of the scale control additive was added to 50 mL of solution L and mixed thoroughly. The pH of the test water was maintained between 0.9 - 1.1. To this mixture, 50 mL of solution M was added and mixed for 2 hours at the desired temperature (50 °C), on completion the solutions were filtered and the filtrate was titrated with 0.2 M EDTA-Na4 solution using CalVer 2 as indicator to determine the soluble calcium concentration. The results of these tests are summarized in table 5.
Table 5. Effect of low molecular weight polymer dispersant and BHMTAP blend No. Additive Dose, ppm % Inhibition 1 0 40% 2* BHMTAP 2 42% 3* BHMTAP 5 44% 4 BHMTAP 10 49% 5 BHMTAP 25 58% 6 BHMTAP 50 82% 7* Additive A 2 41% 8* Additive A 5 43% 9 * Additive A 10 44% 10 Additive A 25 51% 11 Additive A 50 68% 12* Additive B 2 41% 13* Additive B 5 42% 14* Additive B 10 44% 15 Additive B 25 53% 16 Additive B 50 68% 17* Additive C 2 41% 18* Additive C 5 43% 19 * Additive C 10 44% 20 Additive C 25 56% 21 Additive C 50 83% Additive A = poly(AA/MA) + BHMTAP (1:3 w/w), Additive B = poly(SVS) + BHMTAP (1:3 w/w) and Additive C = KEMGUARD® 269 (from Kemira) + BHMTAP (1:3 w/w)
*Reference Example - The effect of BHMTAP and its blends with polymeric dispersants as crystal habit modifier was studied by forcing scale formation with and without additive treatment. Scale formation with additive treatment was enhanced by using mimic water with mixed transition elements and by extending the experimental time. The crystal morphology of the obtained scale was observed under scanning electron microscope and the images are shown in
Figs. 2-5 . The scale obtained for the blank experiment (without any additive treatment) showed rod-shaped crystals (Fig. 2 ), whereas scale obtained with 100 ppm BHMTAP treatment showed significant change in crystal morphology (Fig 3 ). Similarly, the scale obtained using 50 ppm of Additive C of Example 6 (1:3 w/w blend of KEMGUARD® 269 and BHMTAP) (Fig 4 ) or Additive A of Example 6 (poly(AA/MA) and BHMTAP) (Fig 5 ) showed smaller crystals. This sludge like scale is less prone to accumulate and adhere on surface or to form deposits. - The scanning electron microscope observations can be further supported by particle size and aspect ratio measurement data shown in table 6. This data further suggests with increasing BHMTAP dosage the minimum particle size of the gypsum decreases.
Table 6: Morphologi G3i measurements on calcium sulfate scale obtained with BHMTAP treatment Blank 5 ppm BHMTAP* 50 ppm BHMTAP Length minimum (µm) 6.74 6.11 6.09 Length Maximum (µm) 681.57 830.42 905.52 Length Mean (µm) 54.7 46.54 41.75 90% particles are < (µm) 116.38 103.69 99.50 Mean aspect ratio 0.352 0.442 0.508 *Reference Example
No. | Additive | Dose, ppm | Temperature, ° | % Inhibition | |
1* | | 25 | 50 | 10 | |
2* | | 50 | 50 | 27 | |
3* | | 25 | 50 | 17 | |
4 | HMDTMPA | 100 | 50 | 76 | |
5 | | 10 | 50 | 82 | |
6 | BHMTAP | 100 | 50 | 92 |
*Reference Example |
Claims (9)
- Use of a scale control agent for inhibiting scale formation or deposition in highly acidic aqueous systems, the scale control agent comprising organic phosphonate, wherein the organic phosphonate is bis(hexamethylenetriaminepenta (methylenephosphonic acid)) (BHMTAP) and the organic phosphonate is in an amount of from 10 ppm to 100 ppm of the total aqueous system; and wherein the highly acidic aqueous system has a pH less than 2.
- The use of Claim 1 wherein the scale control agent further comprises inorganic phosphonates.
- The use of Claim 1 wherein the scale control agent further comprises a polymer.
- The use of Claim 3 wherein the polymer is a low molecular weight polymeric dispersant and comprises one or more than one functionality selected from the group consisting of carboxylic acid, sulfonic acid, phosphonic acid, alcohol, amide and salts thereof.
- A process for inhibiting or preventing the formation of scale on a substrate having at least one surface in contact with a highly acidic aqueous system comprising adding a scale control agent to the highly acidic aqueous system in an effective amount to inhibit the formation of scale on the surface, wherein an organic phosphonate which is contained in the scale control agent is bis(hexamethylenetriaminepenta (methylenephosphonic acid)) (BHMTAP) and is added to the highly acidic aqueous system in an amount of from 10 ppm to 100 ppm and wherein the highly acidic aqueous system has a pH less than 2.
- The process of Claim 5 wherein the scale comprises calcium sulfate.
- The process of Claim 5 wherein the scale control agent further comprises an inorganic phosphonate.
- The process of Claim 5 wherein the scale control agent further comprises a polymer.
- The process of Claim 8 wherein the polymer comprises a functionality selected from the group consisting of carboxylic acid, sulfonic acid, alcohol, amide and salts thereof.
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US11535911B2 (en) | 2019-10-29 | 2022-12-27 | Solenis Technologies, L.P. | Method for reducing formation of CaSO4 and Fe2O3 containing deposits in a pressure oxidation autoclave and/or adjacent circuits during pressure oxidation of gold-containing ore |
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US3633672A (en) * | 1970-05-11 | 1972-01-11 | Dow Chemical Co | Inhibition of deposition of scale |
US6173780B1 (en) * | 1996-03-15 | 2001-01-16 | Bp Chemicals Limited | Process for increasing effectiveness of production chemicals by reducing number of squeezing and shut-in operations required to increase production rate from an oil well |
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US4676832A (en) * | 1984-10-26 | 1987-06-30 | Halliburton Company | Set delayed cement compositions and methods of using the same |
US6355214B1 (en) * | 1999-06-16 | 2002-03-12 | Hercules Incorporated | Methods of preventing scaling involving inorganic compositions, and inorganic compositions therefor |
US6333005B1 (en) * | 1999-06-16 | 2001-12-25 | Hercules Incorporated | Methods of preventing scaling involving inorganic compositions in combination with copolymers of maleic anhydride and isobutylene, and compositions therefor |
EP1716083A4 (en) * | 2004-02-13 | 2010-05-26 | Gen Electric | Desalination scale inhibitors |
US8513176B2 (en) * | 2006-08-02 | 2013-08-20 | Ch2O Incorporated | Disinfecting and mineral deposit eliminating composition and methods |
EP1887011A1 (en) * | 2006-08-09 | 2008-02-13 | Thermphos Trading GmbH | Alpha amino acid phosphonic acid compounds, method of preparation and use thereof |
EP1886976A1 (en) * | 2006-08-09 | 2008-02-13 | Thermphos Trading GmbH | Method of scale inhibition |
US20090294373A1 (en) * | 2008-05-30 | 2009-12-03 | Gill Jasbir S | Inhibition of water formed scale in acid conditions |
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US8138129B2 (en) * | 2009-10-29 | 2012-03-20 | Halliburton Energy Services, Inc. | Scale inhibiting particulates and methods of using scale inhibiting particulates |
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US3633672A (en) * | 1970-05-11 | 1972-01-11 | Dow Chemical Co | Inhibition of deposition of scale |
US6173780B1 (en) * | 1996-03-15 | 2001-01-16 | Bp Chemicals Limited | Process for increasing effectiveness of production chemicals by reducing number of squeezing and shut-in operations required to increase production rate from an oil well |
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